Skip to main content
SpringerLink
Log in

Confined polymerization: RATRP of GMA in the bicontinuous PolyHIPE

  • Original Paper
  • Published:
Journal of Polymer Research Aims and scope Submit manuscript

Abstract

Controlled free radical polymerization in confined spaces has great potential for obtaining new materials with specific properties and predetermined structures. In this work, polymerized high internal phase emulsion (PolyHIPE) monoliths with bicontinuous structure were synthesized and used as confined reactors for reverse atom transfer radical polymerization (RATRP) of glycidyl methacrylate (GMA). Compared to PGMAs by conventional polymerization, the PGMA obtained in the PolyHIPE exhibits a larger molecular weight, higher glass transition temperature (Tg) and a higher isotactic configuration. The proportion of isotactic configuration in the PGMAs polymerized in the PolyHIPE increased notably, with the highest reaching 65%. All the results exerted evidence for the confining effect of PolyHIPE to the RATRP of GMA. In particular, the PolyHIPE with the largest surface area showed the most significant confining effect. The PGMA obtained within it exhibited the largest molecular weight, the highest isotactic configuration ratio, and the highest Tg.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

Similar content being viewed by others

References

  1. Cheng S, Holt AP, Wang H, Fan F, Bocharova V, Martin H, Etampawala T, White BT, Saito T, Kang N-G (2016) Unexpected molecular weight effect in polymer nanocomposites. Phys Rev Lett 116(3):038302

    Article  PubMed  Google Scholar 

  2. Bruner C, Dauskardt R (2014) Role of molecular weight on the mechanical device properties of organic polymer solar cells. Macromolecules 47(3):1117–1121

    Article  CAS  Google Scholar 

  3. Uemura T, Washino G, Kitagawa S, Takahashi H, Yoshida A, Takeyasu K, Takayanagi M, Nagaoka M (2015) Molecular-level studies on dynamic behavior of oligomeric chain molecules in porous coordination polymers. J Phys Chem C 119(37):21504–21514

    Article  CAS  Google Scholar 

  4. Distefano G, Suzuki H, Tsujimoto M, Isoda S, Bracco S, Comotti A, Sozzani P, Uemura T, Kitagawa S (2013) Highly ordered alignment of a vinyl polymer by host–guest cross-polymerization. Nat Chem 5(4):335–341

    Article  CAS  PubMed  Google Scholar 

  5. Kitao T, Bracco S, Comotti A, Sozzani P, Naito M, Seki S, Uemura T, Kitagawa S (2015) Confinement of single polysilane chains in coordination nanospaces. J Am Chem Soc 137(15):5231–5238

    Article  CAS  PubMed  Google Scholar 

  6. Helms B, Guillaudeu SJ, Xie Y, McMurdo M, Hawker CJ, Fréchet JM (2005) One-pot reaction cascades using star polymers with core-confined catalysts. Angew Chem Int Edit 44(39):6384–6387

    Article  CAS  Google Scholar 

  7. Cotanda P, Petzetakis N, O’Reilly RK (2012) Catalytic polymeric nanoreactors: more than a solid supported catalyst. Mrs Commun 2(4):119–126

    Article  CAS  Google Scholar 

  8. Uemura T, Yanai N, Kitagawa S (2009) Polymerization reactions in porous coordination polymers. Chem Soc Rev 38(5):1228–1236

    Article  CAS  PubMed  Google Scholar 

  9. Comotti A, Bracco S, Mauri M, Mottadelli S, Ben T, Qiu S, Sozzani P (2012) Confined polymerization in porous organic frameworks with an ultrahigh surface area. Angew Chem 124(40):10283–10287

    Article  Google Scholar 

  10. Cucinotta F, Carniato F, Paul G, Bracco S, Bisio C, Caldarelli S, Marchese L (2011) Incorporation of a semiconductive polymer into mesoporous SBA-15 platelets: toward new luminescent hybrid materials. Chem Mater 23(11):2803–2809

    Article  CAS  Google Scholar 

  11. Uemura T, Yanai N, Watanabe S, Tanaka H, Numaguchi R, Miyahara MT, Ohta Y, Nagaoka M, Kitagawa S (2010) Unveiling thermal transitions of polymers in subnanometre pores. Nat Commun 1(1):1–8

    Article  CAS  Google Scholar 

  12. El-Sawy AM, Gemeay AH, Helal AS, Salem MA (2021) Catalytic degradation of methylene blue in aqueous solution by H2O2 and SiO2-NH2-Cu (II)@ SiO2 nanoparticles as catalyst. J Mol Liq 341:117422

    Article  CAS  Google Scholar 

  13. Liu Y, Liu P, Gao S, Wang Z, Luan P, González-Sabín J, Jiang Y (2021) Construction of chemoenzymatic cascade reactions for bridging chemocatalysis and Biocatalysis: Principles, strategies and prospective. Chem Eng J 420:127659

    Article  CAS  Google Scholar 

  14. Yang H, Pu H, Gong F (2016) Attapulgite grafted with polystyrene via a simultaneous reverse and normal initiation atom transfer radical polymerization. J Polym Sci Pol Chem 54(11):1508–1516

    Article  CAS  Google Scholar 

  15. Ma J, Zhang H (2014) Preparation and characterization of poly (methyl methacrylate)/SiO2 organic–inorganic hybrid materials via RAFT-mediated miniemulsion Polymerization. J Polym Res 21(11):1–9

    Article  Google Scholar 

  16. Zetterlund PB (2011) Controlled/living radical polymerization in nanoreactors: compartmentalization effects. Polym Chem 2(3):534–549

    Article  CAS  Google Scholar 

  17. Zetterlund PB, D’hooge DR (2019) The nanoreactor concept: kinetic features of compartmentalization in dispersed phase polymerization. Macromolecules 52(21):7963–7976

    Article  CAS  Google Scholar 

  18. Chen M, Qin L, Wei Y, Liu Y, Zhang F (2019) Confinement effect of mesoporous silica reactors on electron transfer atom transfer radical polymerization of styrene. J Porous Mater 26(1):7–17

    Article  Google Scholar 

  19. Uemura T, Ono Y, Kitagawa K, Kitagawa S (2008) Radical polymerization of vinyl monomers in porous coordination polymers: Nanochannel size effects on reactivity, molecular weight, and stereostructure. Macromolecules 41(1):87–94

    Article  CAS  Google Scholar 

  20. Alqarni Y, Ishizuka F, Bell TD, Tabor RF, Zetterlund PB, Saito K (2020) Confined polymerisation of bis-thyminyl monomers within nanoreactors: towards molecular weight control. Polym Chem 11(26):4326–4334

    Article  CAS  Google Scholar 

  21. Renggli K, Sauter N, Rother M, Nussbaumer MG, Urbani R, Pfohl T, Bruns N (2017) Biocatalytic atom transfer radical polymerization in a protein cage nanoreactor. Polym Chem 8(14):2133–2136

    Article  CAS  Google Scholar 

  22. Cameron N R, P Krajnc, M S Silverstein (2011) Colloidal templating. Porous Polymers 119–172

  23. Cameron N, Sherrington D (1996) High internal phase emulsions (HIPEs)—Structure, properties and use in polymer preparation. Biopolymers Liquid Crystalline Polymers Phase Emulsion 163–214

  24. Wang M, Wang M, Zhu Y, Zhang S, Chen J (2019) Enzyme immobilized millimeter-sized polyHIPE beads with easy separability and recyclability. React Chem Eng 4(6):1136–1144

    Article  CAS  Google Scholar 

  25. Jurjevec S, Žerjav G, Pintar A, Žagar E, Kovačič S (2021) Tunable poly (aryleneethynylene) networks prepared by emulsion templating for visible-light-driven photocatalysis. Catal Today 361:146–151

    Article  CAS  Google Scholar 

  26. Yang L, Jiang C, Yan J, Shen Y, Chen Y, Xu L, Zhu H (2020) Structuring the reduced graphene oxide/polyHIPE foam for piezoresistive sensing via emulsion-templated polymerization. Compos Part A-Appl S 134:105898

    Article  CAS  Google Scholar 

  27. Sun P, Yang S, Sun X, Wang Y, Jia Y, Shang P, Tian H, Li G, Li R, Zhang X (2019) Preparation of PolyHIPE scaffolds for 3D cell culture and the application in cytotoxicity evaluation of cigarette smoke. Polymers-Basel 11(6):959

    Article  CAS  PubMed Central  Google Scholar 

  28. Abebe MW, Kim H (2022) Methylcellulose/tannic acid complex particles coated on alginate hydrogel scaffold via Pickering for removal of methylene blue from aqueous and quinoline from non-aqueous media. Chemosphere 286:131597

    Article  CAS  PubMed  Google Scholar 

  29. Koler A, Kolar M, Jeřábek K, Krajnc P (2021) Influence of Functional Group Concentration on Hypercrosslinking of Poly (vinylbenzyl chloride) PolyHIPEs: Upgrading Macroporosity with Nanoporosity. Polymers-Basel 13(16):2721

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  30. Hobiger V, Zahoranova A, Baudis S, Liska R, Krajnc P (2021) Thiol-Ene Cross-linking of Poly (ethylene glycol) within high internal phase emulsions: Degradable hydrophilic PolyHIPEs for controlled drug release. Macromolecules 54(22):10370–10380

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  31. Kopač T, Lisac A, Mravljak R, Ručigaj A, Krajnc M, Podgornik A (2021) Bacteriophage Delivery Systems Based on Composite PolyHIPE/Nanocellulose Hydrogel Particles. Polymers-Basel 13(16):2648

    Article  PubMed  PubMed Central  Google Scholar 

  32. Kramer S, Cameron NR, Krajnc P (2021) Porous polymers from high internal phase emulsions as scaffolds for biological applications. Polymers-Basel 13(11):1786

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  33. Chen M, Sun F, Xu W, Zhou L, Zhang F (2016) Polymerization of MMA by RATRP in the confined space of polyHIPEs with varied internal phase contents. J Mater Sci 51(11):5113–5121

    Article  CAS  Google Scholar 

  34. Roscoe SB, Frechet JM, Walzer JF, Dias AJ (1998) Polyolefin spheres from metallocenes supported on noninteracting polystyrene. Science 280(5361):270–273

    Article  CAS  PubMed  Google Scholar 

  35. Sun F, Xu W, Chen M, Zhang F (2014) Polymerization of MMA in polyHIPEs by RATRP. J Polym Res 21(12):1–8

    Article  Google Scholar 

  36. Kashiwagi T, Inaba A, Brown JE, Hatada K, Kitayama T, Masuda E (1986) Effects of weak linkages on the thermal and oxidative degradation of poly (methyl methacrylates). Macromolecules 19(8):2160–2168

    Article  CAS  Google Scholar 

  37. Bovey F (1962) Polymer NMR spectroscopy. VI. Methyl methacrylate–styrene and methyl methacrylate–α‐methylstyrene copolymers. J Polym Sci 62(173):197–209

Download references

Author information

Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, Northwestern Polytechnical University, No. 127, West Youyi Road, Xi’an, Shaanxi, 710072, China

    Qianwen Chen, Jia Li, Ganggang Dong, Zongting Zhu, Qiuyu Zhang & Dezhong Yin

Authors
  1. Qianwen Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jia Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Ganggang Dong
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Zongting Zhu
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Qiuyu Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Dezhong Yin
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Dezhong Yin.

Ethics declarations

Confict of interest

The authors declare no conflict of interest.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Chen, Q., Li, J., Dong, G. et al. Confined polymerization: RATRP of GMA in the bicontinuous PolyHIPE. J Polym Res 29, 490 (2022). https://doi.org/10.1007/s10965-022-03328-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s10965-022-03328-4

Keywords

Search

Navigation